CN105308147A - Flexible visor having anti-fogging properties and anti-fogging coating compositions - Google Patents

Flexible visor having anti-fogging properties and anti-fogging coating compositions Download PDF

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Publication number
CN105308147A
CN105308147A CN201480033306.5A CN201480033306A CN105308147A CN 105308147 A CN105308147 A CN 105308147A CN 201480033306 A CN201480033306 A CN 201480033306A CN 105308147 A CN105308147 A CN 105308147A
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layer
weight
transparent
polymer
composite
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CN201480033306.5A
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CN105308147B (en
Inventor
D·马宗达
R·C·赫斯切
J·P·罗素
G·T·巴斯
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Saint Gobain Performance Plastics Corp
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Saint Gobain Performance Plastics Corp
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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
    • C09D175/04—Polyurethanes
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B27/08—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/40—Layered products comprising a layer of synthetic resin comprising polyurethanes
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
    • B32B7/04—Interconnection of layers
    • B32B7/12—Interconnection of layers using interposed adhesives or interposed materials with bonding properties
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/30—Low-molecular-weight compounds
    • C08G18/38—Low-molecular-weight compounds having heteroatoms other than oxygen
    • C08G18/3819—Low-molecular-weight compounds having heteroatoms other than oxygen having nitrogen
    • C08G18/3842—Low-molecular-weight compounds having heteroatoms other than oxygen having nitrogen containing heterocyclic rings having at least one nitrogen atom in the ring
    • C08G18/3851—Low-molecular-weight compounds having heteroatoms other than oxygen having nitrogen containing heterocyclic rings having at least one nitrogen atom in the ring containing three nitrogen atoms in the ring
    • C08G18/3853—Low-molecular-weight compounds having heteroatoms other than oxygen having nitrogen containing heterocyclic rings having at least one nitrogen atom in the ring containing three nitrogen atoms in the ring containing cyanurate and/or isocyanurate groups
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L75/00—Compositions of polyureas or polyurethanes; Compositions of derivatives of such polymers
    • C08L75/04—Polyurethanes
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J175/00—Adhesives based on polyureas or polyurethanes; Adhesives based on derivatives of such polymers
    • C09J175/04—Polyurethanes
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B1/00—Optical elements characterised by the material of which they are made; Optical coatings for optical elements
    • G02B1/10—Optical coatings produced by application to, or surface treatment of, optical elements
    • G02B1/14—Protective coatings, e.g. hard coatings
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B27/00—Optical systems or apparatus not provided for by any of the groups G02B1/00 - G02B26/00, G02B30/00
    • G02B27/0006—Optical systems or apparatus not provided for by any of the groups G02B1/00 - G02B26/00, G02B30/00 with means to keep optical surfaces clean, e.g. by preventing or removing dirt, stains, contamination, condensation
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2250/00—Layers arrangement
    • B32B2250/05—5 or more layers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2250/00—Layers arrangement
    • B32B2250/24—All layers being polymeric
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2250/00—Layers arrangement
    • B32B2250/24—All layers being polymeric
    • B32B2250/246—All polymers belonging to those covered by groups B32B27/32 and B32B27/30
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2255/00—Coating on the layer surface
    • B32B2255/10—Coating on the layer surface on synthetic resin layer or on natural or synthetic rubber layer
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2255/00—Coating on the layer surface
    • B32B2255/26—Polymeric coating
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2255/00—Coating on the layer surface
    • B32B2255/28—Multiple coating on one surface
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/40—Properties of the layers or laminate having particular optical properties
    • B32B2307/412—Transparent
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/70—Other properties
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/70—Other properties
    • B32B2307/728—Hydrophilic
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2551/00—Optical elements
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B33/00—Layered products characterised by particular properties or particular surface features, e.g. particular surface coatings; Layered products designed for particular purposes not covered by another single class
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G2170/00—Compositions for adhesives
    • C08G2170/80—Compositions for aqueous adhesives
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D167/00—Coating compositions based on polyesters obtained by reactions forming a carboxylic ester link in the main chain; Coating compositions based on derivatives of such polymers
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K3/00—Materials not provided for elsewhere
    • C09K3/18—Materials not provided for elsewhere for application to surfaces to minimize adherence of ice, mist or water thereto; Thawing or antifreeze materials for application to surfaces
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/31504—Composite [nonstructural laminate]
    • Y10T428/31551—Of polyamidoester [polyurethane, polyisocyanate, polycarbamate, etc.]
    • Y10T428/31573—Next to addition polymer of ethylenically unsaturated monomer
    • Y10T428/3158—Halide monomer type [polyvinyl chloride, etc.]

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Physics & Mathematics (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Wood Science & Technology (AREA)
  • Materials Engineering (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Polymers & Plastics (AREA)
  • Optics & Photonics (AREA)
  • General Physics & Mathematics (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Laminated Bodies (AREA)
  • Materials Applied To Surfaces To Minimize Adherence Of Mist Or Water (AREA)
  • Paints Or Removers (AREA)

Abstract

The present disclosure is directed to transparent composites having anti-fogging properties and anti-fog coating compositions for providing anti-fogging properties. The anti-fogging layers can contain an adhesive polymer, a hard polymer, and a hydrophilic polymer, wherein the adhesive polymer, hard polymer, and hydrophilic polymers are different. In further embodiments, composites are described including a substrate layer; a first adhesive layer; a first transparent layer; a second adhesive layer; a second transparent layer; and an anti-fog layer.

Description

There is flexible shading plate and the anti fogging coating composite of anti-fog performance
Technical field
The present invention relates to the tinted shade and anti fogging coating composite with anti-fog performance, more particularly, relate to the anti fogging coating composite of tinted shade and the combination of the different polymkeric substance of use with anti-fog performance.
Background technology
Antifog composition and the tinted shade containing antifog composition are known in the art.Such as, the polyurethane coating composition with hydrophilic nmature has been used to provide anti-fog effect.But hydrophilic polyurethane is usually soft and be clamminess, thus cause antifogging coating to the less desirable adhesion in various surface.Like this tackiness may to cause in the coating of flexible compound tinted shade, assembling or actual use procedure applied layer from the leafing of base material.In addition, when attempting improvement and being used alone the shortcoming of hydrophilic polyurethane, characteristic such as the transparency, mist degree, hardness, scratch resistance will be subject to negative impact usually.
Therefore, still need not leafing and there is good hardness and excellent transparency there is anti-fog properties new tinted shade matrix material.
Accompanying drawing explanation
Embodiment is illustrated by way of example and is not limited in accompanying drawing.
Fig. 1 shows the cross section signal of compound tinted shade according to an embodiment of the invention.
Fig. 2 shows the cross section signal of compound tinted shade according to another embodiment of the invention.
Those of skill in the art should be understood that key element in accompanying drawing for simple and clear for the purpose of signal and might not drawing in proportion.Such as, the size of some key elements in accompanying drawing will may have relative to other amplifies with the understanding helping improve embodiments of the invention.
Embodiment
Hereafter description taken together with the accompanying drawings provides to help to understand instruction disclosed herein.Discussion hereafter will focus on particular implementation and the embodiment of instruction.This focuses on provides to help to describe described instruction and should not be construed as the scope or suitability that limit instruction.But, other embodiment can be used based on instruction disclosed in such as the application.
Term " comprises ", " comprising ", " having " or its other modification any are intended to contain comprising of nonexcludability.Such as, comprise the method for feature list, goods or device be not necessarily only limitted to these features but that clearly do not list or that these class methods, goods or device are intrinsic further feature can be comprised.In addition, unless explicitly stated otherwise on the contrary, otherwise "or" refer to comprising property or and nonexcludability or.Such as, condition A or B is met by one of any in following: A is true (or existence) and B is false (or not existing), A is false (or not existing) and B is true (or existence), and A and B is very (or existence).
In addition, the use of " " or " one " is used for describing key element described herein and parts.Do like this and be only conveniently and provide the general significance of scope of the present invention.This description is understood to include one (individual), at least one (individual), or odd number also comprises plural number, and vice versa, unless be clearly other meaning.Such as, when describing single item in this article, a more than item can be used for replacing single item.Similarly, when describing a more than item in this article, single item can replace a more than item.
Unless otherwise defined, all technology used herein and scientific terminology have understood identical implication usual with one skilled in the art of the present invention.Material, method and example be only schematic and be not intended to restriction.In the scope do not described herein, the many details about certain material and processing behavior are conventional and the textbook be found in clear anti-fog field of compound material and other source.
Disclosure below describes antifog composition and has the matrix material of antifog composition, wherein said antifog composition comprises the Combination nova of at least three kinds of different polymkeric substance, and the present inventor has been surprised to find these different polymkeric substance and produces collaborative improvement in the characteristic comprising antifog, physical strength, adhesion and the transparency.Described matrix material can especially for the application comprising tinted shade, window etc.Based on embodiment described below, concept will be better understood, and these embodiments are illustrated and do not limit the scope of the invention.
One embodiment of the present of invention relate to matrix material 10, and as shown in fig. 1, it comprises stratum basale 20 and anti-fog layer 50.Anti-fog layer 50 can directly be close to stratum basale 20 and arrange.In other embodiments, as hereafter will discussed in more detail, matrix material can contain other layer containing other interlayer and on or below stratum basale 20 and anti-fog layer 50 between stratum basale 20 and anti-fog layer 50.Usually, anti-fog layer 50 by for matrix material skin and be exposed to environment.In certain embodiments, anti-fog layer will be set up in the composite so that it is suitable in the face of human user.Such as, as hereafter will discussed in more detail, a kind of matrix material of form is tinted shade structure, and the layer that anti-fog layer can be arranged on matrix material is interior so that it is suitable in the face of user.
A special example of the matrix material with other layer has been shown in Fig. 2.Matrix material 100 can contain stratum basale 200, first binder layer 210, first transparent layer 220, second binder layer 230, second transparent layer 240 and anti-fog layer 250.Each in aforementioned layers can arrange as shown in Figure 2 and be in direct contact with one another.In addition, in other embodiments, other layer can be set between layer illustrated in fig. 2.As discussed above, usually, in tinted shade structure situation, anti-fog layer can be made to be suitable in use in the face of user.Therefore, in a particular embodiments, direct contiguous second transparent layer 240 of anti-fog layer 250 can be made and contact with the second transparent layer 240.Other special embodiment of the present invention relates to anti fogging coating composite.This type of anti fogging coating composite can containing the crosslinkable network of polymkeric substance, and described polymkeric substance comprises binder polymer, hard polymer and hydrophilic polymer, and wherein said binder polymer, hard polymer and hydrophilic polymer are different.
The example of some layer of present description matrix material and the component of characteristic and anti-fog layer.Should be understood that any description of antifogging coating is also applicable to anti fogging coating composite.
Stratum basale can be multiple different material, comprises such as transparent plastics, glass, metal or pottery.In a preferred embodiment, substrate is flexible.Such as, flexible substrates is the substrate that can bend repeatedly or bend and do not rupture.In certain embodiments, substrate can comprise flexible plastic material as polyester, comprises polyethylene terephthalate (PET), PEN (PEN), polyester ionomer, amorphous polyester is as amorphous glycol modification PET (PETG), polyethersulfone (PES), polycarbonate (PC), polysulfones, resol, epoxy resin, polyether ester, polyetheramides, nitrocellulose, rhodia is as cellulose triacetate (TAC), poly-(vinyl acetate), polystyrene, polyolefine (comprising polyolefin ionomers), polymeric amide, urethane, poly-thiocarbamate, polyacrylonitrile, poly-(methyl (x-methacrylic ester)), aliphatic series or cyclic polyolefin, polyarylester (PAR), polyetherimide (PEI), polyethers sulfoxide (PES), polyimide (PI), poly-(ether ether ketone) (PEEK), poly-(ether ketone) (PEK) and poly-(methyl methacrylate) and various acrylate/methacrylate multipolymer (PMMA), polyvinyl chloride (PVC), various fluoropolymer, the various polymkeric substance based on silicone, space polymkeric substance (comprising foam of polymers), microvoid polymkeric substance and poromerics, fabric or their any combination.In a particular embodiments, polyolefine can comprise high density polyethylene(HDPE) (HDPE), Low Density Polyethylene (LDPE) and polypropylene, comprises oriented polypropylene (OPP).Cyclic polyolefin can comprise poly-(two (cyclopentadiene)).Example comprises: the Artong of the JapanSyntheticRubberCo. manufacture of Tokyo; The ZeanorT of the ZeonChemicalsL.P. manufacture of Tokyo; The Topas.RTM of the CelaneseA.G. manufacture of vigorous lattice is cloned with Germany.Arton is poly-(two (cyclopentadiene)) condenses, and it is the film of polymkeric substance.
In other special embodiment, polyester can comprise derived from the condensation of aromatics, alicyclic and aliphatic diol and aliphatic series, aromatics and alicyclic dicarboxylic acid those and can be alicyclic, aliphatic series or aromatic polyester.Alicyclic especially, the example of aliphatic series and aromatic polyester comprises poly-(ethylene glycol terephthalate), poly-(terephthalic acid cyclohexylidene two methylene ester), poly-(laurostearic acid glycol ester), poly-(mutual-phenenyl two acid bromide two alcohol ester), poly-((ethylene naphthalate)), poly-((2,7-naphthalic acid) glycol ester), poly-(m-phthalic acid methyl benzenediol ester), poly-(oxyacetic acid), poly-(succsinic acid glycol ester), poly-(ethylene glycol adipate(EGA)), poly-(sebacic acid glycol ester), poly-(nonane diacid decanediol ester), poly-(sebacic acid glycol ester), poly-(hexanodioic acid decanediol ester), poly-(sebacic acid decanediol ester), poly-(dimethyl propiolactone), poly-(p-hydroxy Benzoic Acid ester) (Ekonol), poly-(hydroxy-benzoic acid glycol ester) (A-tell), poly-(ethylene isophthalate), poly-(terephthalic acid four methylene ester), poly-(terephthalic acid six methylene ester), poly-(terephthalic acid decanediol ester), poly-(terephthalic acid Isosorbide-5-Nitrae-hexanaphthene two methylene ester) (trans), poly-(1,5-(ethylene naphthalate)), poly-(NDA glycol ester), poly-(terephthalic acid Isosorbide-5-Nitrae-cyclohexylidene two methylene ester) (Kodel) (cis) and poly-(terephthalic acid Isosorbide-5-Nitrae-cyclohexylidene two methylene ester) (Kodel) (trans).In a particular embodiments, petchem can be the petchem prepared from the condensation of glycol and aromatic dicarboxylic acid.The signal of such aromatic carboxylic acid has terephthalic acid, m-phthalic acid and α-phthalic acid, 1,3-naphthalene dicarboxylic acids, 1,4-naphthalene dicarboxylic acids, 2,6-naphthalene dicarboxylic acids, 2,7-naphthalene dicarboxylic acids, 4,4'-diphenyldicarboxylic acids, 4,4 '-sulfobenzide dicarboxylic acid, 1,1,3-trimethylammonium-5-carboxyl-3-(p-carboxyl phenyl)-idane, diphenyl ether 4,4 '-dicarboxylic acid, two-to (carboxyl-phenyl) methane etc.In even more particularly embodiment, above-mentioned aromatic dicarboxylic acid can comprise those (as terephthalic acid, m-phthalic acid, phthalic acids) based on phenyl ring.In these acid precursor, terephthalic acid is a kind of special acid precursor.
Fluoropolymer can comprise: tetrafluoroethylene (PTFE), perfluoroalkoxy (PFA), fluorinated ethylene-propylenes (FEP), tetrafluoroethylene, the multipolymer (THV) of R 1216 and vinylidene fluoride, the multipolymer of R 1216 (HFP) and vinylidene fluoride (VDF or VF2), tetrafluoroethylene (TFE), vinylidene fluoride (VDF) and the terpolymer of R 1216 (HFP) and the special chemical article containing perfluoro methyl vinyl ether (PMVE), poly-(ethylene-tetrafluoroethylene) (ETFE), poly(vinylidene fluoride) (PVDF), fluorinated ethylene propylene (PVF), poly-(ethylene-chlorinated) (ECTFE), voltalef (PCTFE), poly-(ethylene-tetrafluoroethylene) fluoropolymer (PETFE), and their combination.Especially, fluoropolymer is very difficult to adhere to the substrate of any layer, particularly anti-fog layer to it without leafing risk.A special advantage of some embodiment of matrix material described herein is adhesivity or the cohesiveness of fluoropolymer layer excellence.This feature also describes with the ability of its not leafing.
In certain embodiments, pvc material can derived from monomeric vinyl chloride by the polymerization of any appropriate technology as suspension polymerization, letex polymerization or mass polymerization.Pvc material can comprise the chlorinated polyvinyl chloride of the cl content with raising.For obtaining required physics and chemistry character and the easiness of processing, pvc material can comprise annexation as thermo-stabilizer, UV stablizer, lubricant, softening agent, processing aid, impact modifying agent, heat modification agent, filler, fire retardant, biocide, whipping agent and smoke suppressor and optionally pigment.
In very special embodiment, base material can comprise: polyvinyl chloride; Polyester is as PET, PEN, PETG, polyester ionomer; Polycarbonate; Fluoropolymer is as ETFE, PFA, FEP, PVDF, THV and PVF; Polyolefine is as PE and PP; Urethane; Rhodia; And glass.
In certain embodiments, when deployed, flexible plastic substrates can strengthen with hard coat.Usually, hard coat is acrylic coatings.Such hard coat usually has the thickness of 1 to 15 micron as 2 to 4 microns and provides by thermal initiation or by the radical polymerization that uv-radiation causes by suitable polymerizable material.Depend on substrate, different hard coats can be used.When substrate be polyester or Arton time, useful especially hard coat is for being called the coating of " Lintec ".Lintec contains polyester acrylate and the colloid silica of UV solidification.When being deposited on Arton, outside dehydrogenation, it has the surface composition of 35 atom %C, 45 atom %O and 20 atom %Si.Another useful especially hard coat is the acrylic coatings of being sold with trade(brand)name " Terrapin " by the TekraCorporation of new Berlin, Wisconsin State.
See Fig. 2 again, some embodiment can comprise the other polymer layer except stratum basale in the composite.In such embodiments, matrix material such as can contain binder layer between any polymer layer.
In certain embodiments, binder layer can comprise one or more in water-soluble polymers, lyophilic colloid or insoluble polymer, latex or dispersion.In a particular embodiments, binder layer can contain from ethylenically unsaturated monomers polymkeric substance as obtained in vinylbenzene, styrene derivatives, acrylic or methacrylic acid and their derivative, alkene, (methyl) vinyl cyanide, methylene-succinic acid and derivative, toxilic acid and derivative thereof, vinyl halide, vinyl acetate, vinylidene halide, epoxide, carbamate, imines, polyester, fluoropolymer or their combination or interpretation.
Specially suitable fluoropolymer can comprise: tetrafluoroethylene (PTFE), perfluoroalkoxy (PFA), fluorinated ethylene-propylenes (FEP), the multipolymer (THV) of tetrafluoroethylene, R 1216 and vinylidene fluoride, poly-(ethylene-tetrafluoroethylene) (ETFE), poly(vinylidene fluoride) (PVDF), fluorinated ethylene propylene (PVF), poly-(ethylene-chlorinated) (ECTFE), voltalef (PCTFE) and their combination.
In a particular embodiments, binder layer can from the aqueous dispersion of polycondensate as urethane and polyester.
Also can be to describe the component of binder layer with its second-order transition temperature.In a particular embodiments, binder layer can comprise second-order transition temperature (Tg) not higher than 60 degrees Celsius, not higher than 20 degrees Celsius, not higher than 10 degrees Celsius, not even higher than the polymkeric substance of 0 degree Celsius.These second-order transition temperatures will guarantee the abundant flowing of binder layer in lamination.
Another approach describing binder layer is by the quantification of its adhesive effect by peeling strength test.Stripping strength can be measured according to ASTMD1876.In certain embodiments, the first binder layer, the second binder layer or their combination can have at least about 2 pounds of every linear inches (PLI), at least about 3PLI, at least about 4PLI or even at least about the stripping strength of 5PLI between adjacent sheet material.Especially, adjacent sheet material can be described herein those, as stratum basale, the first transparent layer, the second transparent layer or their combination.
Binder layer can have at least 0.1 micron, at least 0.5 micron or the even thickness of at least 1 micron.Binder layer can have and is not more than 100 microns, is not more than 50 microns, is not more than 10 microns or be not even greater than the thickness of 8 microns.In addition, binder layer can have the thickness in the scope of any above-mentioned minimum and maximum value, 0.1 micron to about 100 microns, about 0.5 micron to about 50 microns or even about 1 micron to about 10 microns according to appointment.
As discussed above, matrix material can contain the other layer except stratum basale, as the first transparent layer and the second transparent layer.First transparent layer and/or the second transparent layer can be materials different in a large number, comprise for stratum basale describe those.In certain embodiments, the first transparent layer can containing identical material with the second transparent layer.In other embodiments, the first transparent layer and the second transparent layer can be different.In a particular embodiments, the first and/or second transparent layer can contain polymkeric substance.However, it should be understood that the first and/or second transparent layer can comprise glass, pottery, metal or other suitable material any for any reason.Such as, the first and second transparent layers can be above for stratum basale describe any material.
First transparent layer and/or the second transparent layer can comprise such as transparent plastics as above as stratum basale describe those.In a particular embodiments, the first transparent layer and/or the second transparent layer with such as above for stratum basale describe identical.For the first transparent layer and/or the second transparent layer, most preferred material comprises: polyvinyl chloride; Polyester is as PET, PEN, PETG, polyester ionomer; Polycarbonate; Fluoropolymer is as ETFE, PFA, FEP, THV; Polyolefine is as PE and PP; Rhodia; And glass.
Stratum basale and/or the first transparent layer and/or the second transparent layer by any measure known in the art as extruded, coextrusion, molded, blowing, orientation, laminated, curtain coating, calendering, coating, the generation such as thermoforming.In a preferred embodiment, stratum basale and/or the first transparent layer and/or the second transparent layer can contain self-supporting sheet material.
Stratum basale and/or the first transparent layer and/or the second transparent layer can comprise any additive as charge control agent, conductive particle or polymkeric substance, linking agent or stiffening agent, solubility and/or solid particle dye, antifogging agent, inorganic or organic filler, dispersion agent, lubricant, softening agent, antioxidant, space agent, tinting material or staining agent, alligatoring agent, surface slip agent, UV absorption agent, index-matching material, releasing agent, fire retardant and other additive well known in the art.
In a particular embodiments, stratum basale and/or the first transparent layer and/or the second transparent layer and especially fluoropolymer layer can have any amount of undercoat or surface treatment to improve coating performance and/or adhesion.Such undercoat can comprise acrylic acid or the like, urethane, polyester, vinylidene halide, polyolefine, epoxide, silane etc.Surface treatment can comprise flame, plasma body and Corona discharge Treatment, ultraviolet radiation treatment, ozonize, electron beam treatment, chemical treatment etc.
The useful especially surface treatment of one being preferred for fluoropolymer surface is C-process, and it refers to carry out the method for modified surface by corona treatment under the existence of solvent gas as acetone.Be not limited to theory, found that described method provides strong layer-to-layer adhesion between modified fluoropolymer and non-fluoropolymer interface (or second modified fluoropolymer).C-process has been shown in and has been set forth in United States Patent (USP) 6,726,979 and reference wherein in, their instruction is incorporated herein with it in full for all objects.
Anti-fog layer can contain one or more polymkeric substance.In certain embodiments, anti-fog layer can containing at least two kinds of different polymkeric substance, at least three kinds of different polymkeric substance or even at least four kinds of different polymkeric substance.In a preferred embodiment, anti-fog layer is containing the cross-linked network of different polymkeric substance.
The polymkeric substance described in anti-fog layer with some material character will be helpful.In a particular embodiments, anti-fog layer can contain hydrophilic polymer, binder polymer and hard polymer, and wherein each polymkeric substance is different.
The hydrophilic polymer of anti-fog layer can comprise such as polyvinyl alcohol, polyvinyl acetal, polyvinyl acetate (PVA), Polyvinylpyrolidone (PVP), polyethylene oxide, polyacrylamide, polyester, urethane, rhodia, Natvosol, Walocel MT 20.000PV or gelatin or their blend or multipolymer.Hydrophilic polymer can be the polymkeric substance of the hydrophilic segment having main chain and be covalently bound to main chain.
Hydrophilic segment can comprise oxirane, lactone, lactan, silane, acrylamide, alcohol, gelatin or their combination.In a particular embodiments, hydrophilic segment comprises oxirane, lactone, lactan or their combination.
Hydrophilic segment can have at least about 100, at least about 500 or even at least about 1000 molecular weight.In addition, hydrophilic segment can have not higher than about 100000, not higher than about 50000 or not even higher than about 10000 molecular weight.In addition, hydrophilic segment can have the molecular weight in the scope of any above-mentioned minimum and maximum value, and 100 to about 100000, about 500 to about 50000 or even about 1000 to about 10000 according to appointment.
Hydrophilic segment can be hydrophilic polymer weight at least about 1 % by weight, at least about 10 % by weight or even at least about 25 % by weight.In addition, hydrophilic segment can be no more than about 95 % by weight, be no more than about 75 % by weight or even do not exceed about 50 % by weight.In addition, hydrophilic segment can account for the weight percentage in the scope of any above-mentioned minimum and maximum value of hydrophilic polymer, and according to appointment 1 % by weight to about 95 % by weight, about 10 % by weight to about 75 % by weight or even about 25 % by weight to about 50 % by weight.
Based on the overall dry weight of anti-fog layer, hydrophilic polymer higher than about 99.9 % by weight, not higher than about 90 % by weight, not higher than about 80 % by weight or even can be present in anti-fog layer higher than the amount of about 70 % by weight.In other embodiments, based on the overall dry weight of anti-fog layer, hydrophilic polymer at least about 0.01 % by weight, at least about 10 % by weight, at least about 20 % by weight or even can be present in anti-fog layer at least about the amount of 25 % by weight.In addition, based on the overall dry weight of anti-fog layer, hydrophilic polymer can the amount in the scope of any above-mentioned minimum and maximum value be present in anti-fog layer, and according to appointment 0.01 % by weight to about 99.9 % by weight, about 10 % by weight to about 90 % by weight, about 20 % by weight to about 80 % by weight or even about 25 % by weight to about 75 % by weight.
In addition, in certain embodiments, hydrophilic polymer can be the principal polymeric in anti-fog layer.Such as, hydrophilic polymer can be present in anti-fog layer higher than the amount of binder polymer, hard polymer or their combination.
Binder polymer can comprise in water-soluble polymers, lyophilic colloid or insoluble polymer, latex or dispersion one or more.In a particular embodiments, binder polymer can be from ethylenically unsaturated monomers polymkeric substance as obtained in vinylbenzene, styrene derivatives, acrylic or methacrylic acid and their derivative, alkene, (methyl) vinyl cyanide, methylene-succinic acid and derivative, toxilic acid and derivative thereof, vinyl halide, vinyl acetate, vinylidene halide, epoxide, carbamate, imines, polyester, fluoropolymer or their combination or interpretation.
Specially suitable fluoropolymer can comprise: tetrafluoroethylene (PTFE), perfluoroalkoxy (PFA), fluorinated ethylene-propylenes (FEP), the multipolymer (THV) of tetrafluoroethylene, R 1216 and vinylidene fluoride, poly-(ethylene-tetrafluoroethylene) (ETFE), poly(vinylidene fluoride) (PVDF), fluorinated ethylene propylene (PVF), poly-(ethylene-chlorinated) (ECTFE), voltalef (PCTFE) and their combination.
In a particular embodiments, binder polymer can from the aqueous dispersion of polycondensate as urethane and polyester.
Also can be to describe binder polymer with its second-order transition temperature.In a particular embodiments, binder polymer can have not higher than 60 degrees Celsius, not higher than 20 degrees Celsius, not higher than 10 degrees Celsius, not even higher than the second-order transition temperature (Tg) of 0 degree Celsius.These second-order transition temperatures will guarantee the abundant flowing of polymkeric substance in lamination.
Another approach describing binder polymer is by the quantification of its adhesive effect by peeling strength test.Stripping strength is measured according to ASTMD1876.In certain embodiments, binder polymer can have at least about 2 pounds of every linear inches (PLI), at least about 3PLI, at least about 4PLI or even at least about the stripping strength of 5PLI between adjacent sheet material.
In certain embodiments, based on the overall dry weight of anti-fog layer, binder polymer higher than about 90 % by weight, not higher than about 80 % by weight, not higher than about 70 % by weight or even can be present in anti-fog layer higher than the amount of about 60 % by weight.In other embodiments, based on the overall dry weight of anti-fog layer, binder polymer at least about 0.1 % by weight, at least about 10 % by weight, at least about 20 % by weight or even can exist at least about the amount of 25 % by weight.In addition, based on the overall dry weight of anti-fog layer, binder polymer can the amount in the scope of any above-mentioned minimum and maximum value be present in anti-fog layer, and according to appointment 0.1 % by weight to about 90 % by weight, about 10 % by weight to about 80 % by weight, about 20 % by weight to about 70 % by weight or even about 25 % by weight to about 60 % by weight.
In other embodiments, anti-fog layer also can comprise hard polymer.Hard polymer can provide physical strength to anti-fog layer and also help improve the scratch resistance of anti-fog layer.
In certain embodiments, hard polymer can comprise water-soluble polymers, lyophilic colloid or insoluble polymer, latex or dispersion.In a particular embodiments, hard polymer can be from ethylenically unsaturated monomers polymkeric substance as obtained in vinylbenzene, styrene derivatives, acrylic or methacrylic acid and their derivative, alkene, (methyl) vinyl cyanide, methylene-succinic acid and derivative, toxilic acid and derivative thereof, vinyl halide, vinyl acetate, vinylidene halide, epoxide, carbamate, imines, polyester, fluoropolymer or their combination or interpretation.Specially suitable fluoropolymer can comprise: tetrafluoroethylene (PTFE), perfluoroalkoxy (PFA), fluorinated ethylene-propylenes (FEP), the multipolymer (THV) of tetrafluoroethylene, R 1216 and vinylidene fluoride, poly-(ethylene-tetrafluoroethylene) (ETFE), poly(vinylidene fluoride) (PVDF), fluorinated ethylene propylene (PVF), poly-(ethylene-chlorinated) (ECTFE), voltalef (PCTFE) and their combination.
In some other embodiment, hard polymer can comprise the aqueous dispersion of polycondensate as urethane and polyester.
Also can be to describe hard polymer with its hardness.Hardness can use the pencil hardness test measured according to ASTMD3363 to quantize.In embodiment described herein, as measured by ASTMD3363, hard polymer can have at least about H, at least about 2H, pencil hardness at least about 3H.In addition, as measured by ASTMD3363, hard polymer can have not higher than about 9H, not higher than about 8H, not higher than about 7H, not higher than about 6H or not even higher than the pencil hardness of about 5H.In addition, as measured by ASTMD3363, hard polymer can have the pencil hardness in the scope of any above-mentioned minimum and maximum value, and H is to about 9H, about 2H to about 8H or even about 3H to about 7H according to appointment.
Another useful quality describing hard polymer is its 100% modulus.In a particular embodiments, as measured by ASTMD412, hard polymer can have at least about 2000psi, at least about 3000psi or even at least about 100% modulus of 3500psi.In other embodiments, as measured by ASTMD412, hard polymer can have not higher than about 15000psi, not higher than about 10000psi or not even higher than 100% modulus of about 7500psi.In addition, as measured by ASTMD412, hard polymer can have 100% modulus in the scope of any above-mentioned minimum and maximum value, and 2000psi is to about 15000psi, about 3000psi to about 10000psi or even about 3500psi to about 7500psi according to appointment.
Also another available characteristic describing hard polymer is its tensile strength.In a particular embodiments, as measured by ASTMD412, hard polymer can have at least about 3000psi, at least about 4000psi or even at least about the tensile strength of 5000psi.In other embodiments, as measured by ASTMD412, hard polymer can have not higher than about 15000psi, not higher than about 1000psi or not even higher than the tensile strength of about 7500psi.In addition, as measured by ASTMD412, hard polymer can have the tensile strength in the scope of any above-mentioned minimum and maximum value, and 3000psi is to about 15000psi, about 4000psi to about 10000psi or even about 5000psi to about 7500psi according to appointment.
Also another available characteristic describing hard polymer is its elongation at break %.In a particular embodiments, as measured by ASTMD412, when hard polymer can have a fracture at least 100%, fracture time at least about the elongation at break % even at least about 300% when 200% or fracture.In other embodiments, as measured by ASTMD412, extend when hard polymer can have a fracture be no more than 1000%, fracture time extend the elongation at break % extended when being no more than 700% or fracture not even more than 500%.In addition, as measured by ASTMD412, hard polymer can have the elongation at break % in the scope of any above-mentioned minimum and maximum value, as extended about 100% during fracture to about 1000%, about 200% to about 700% or even about 300% to about 500%.
In certain embodiments, based on the overall dry weight of anti-fog layer, hard polymer higher than about 90 % by weight, not higher than about 80 % by weight, not higher than about 70 % by weight or even can be present in anti-fog layer higher than the amount of about 60 % by weight.In other embodiments, based on the overall dry weight of anti-fog layer, hard polymer at least about 0.1 % by weight, at least about 10 % by weight, at least about 20 % by weight or even can exist at least about the amount of 25 % by weight.In addition, based on the overall dry weight of anti-fog layer, hard polymer can the amount in the scope of any above-mentioned minimum and maximum value be present in anti-fog layer, and according to appointment 0.1 % by weight to about 90 % by weight, about 10 % by weight to about 80 % by weight, about 20 % by weight to about 70 % by weight or even about 25 % by weight to about 60 % by weight.
In very special embodiment, anti fogging coating composite and anti-fog layer also can comprise one or more anti (anti-blocking) agent.In a particular embodiments, anti blocking agent can comprise colloid inorganic particle as colloid silica and/or tensio-active agent.
In certain embodiments, colloidal silicas compounds can contain nano particle.In addition, in certain embodiments, colloidal silicas compounds can be substantially transparent.The special example of suitable colloid silica can comprise LudoxAM, and it can be commercially available from WRGraceCo..
When deployed, based on the total weight of anti fogging coating composite or anti-fog layer, colloid silica at least about 1 % by weight, at least about 3 % by weight or even can be present in anti fogging coating composite or anti-fog layer at least about the amount of 7 % by weight.In other embodiments, colloid silica higher than about 50 % by weight, not higher than about 40 % by weight, not higher than about 30 % by weight or even can be present in anti fogging coating composite or anti-fog layer higher than the amount of about 20 % by weight.In the embodiment of going back other, amount in the scope of the minimum and maximum value that colloid silica can anyly provide above is present in anti fogging coating composite or anti-fog layer, according to appointment 1 % by weight to about 50 % by weight, about 3 % by weight to about 40 % by weight or even about 7 % by weight to about 30 % by weight scope in.
About tensio-active agent, in a particular embodiments, tensio-active agent can comprise fluorinated surfactant.In addition, in certain embodiments, tensio-active agent can comprise anion surfactant.In very special embodiment, tensio-active agent can comprise fluorinated anionic tensio-active agent.The suitable example of fluorinated anionic tensio-active agent can comprise and can derive from DuPont tMcapstoneFS-61.
In certain embodiments, based on the total weight of anti fogging coating composite or anti-fog layer, tensio-active agent at least about 0.005 % by weight, at least about 0.01 % by weight or even can be present in anti fogging coating composite or anti-fog layer at least about the amount of 0.03 % by weight.In other embodiments, tensio-active agent higher than about 15 % by weight, not higher than about 10 % by weight, not higher than about 8 % by weight or even can be present in anti fogging coating composite or anti-fog layer higher than the amount of about 2 % by weight.In the embodiment of going back other, amount in the scope of the minimum and maximum value that tensio-active agent can anyly provide above is present in anti fogging coating composite or anti-fog layer, according to appointment 0.005 % by weight to about 15 % by weight, about 0.01 % by weight to about 10 % by weight or even about 0.03 % by weight to about 8 % by weight scope in.
A special advantage of some embodiment of the present invention is to find that above-mentioned antiblocking agent significantly can reduce the adhesion (be also often called as adhesion or be clamminess) of antifogging coating unexpectedly.When the folding composite structure containing anti-fog layer makes two surface contact containing anti-fog layer, as in the personal safety equipment wired up, such antiblocking effect is special needs.When there is not above-mentioned antiblocking agent, such situation may cause two surfaces stick in together and be separated time damage anti-fog layer, particularly when composite structure is stored under the high temperature of more than room temperature.As what illustrate in greater detail in example below, find that above-mentioned antiblocking agent serves the effect significantly reducing adhesion unexpectedly.Correspondingly, in some special embodiment of the present invention, anti-fog layer and/or anti fogging coating composite can contain hydrophilic polymer and antiblocking agent, comprise colloid silica and/or fluorinated anionic tensio-active agent.Therefore, should be understood that in certain embodiments, hard polymer and/or binder polymer can be optional.
In the formation of anti-fog layer or the first and second binder layers, composition can be solvent borne or water-based.For environment reason, preferred waterborne compositions." water-based " refers to that paint medium comprises the water of at least 50 % by weight.
Coating composition or coating can comprise any amount of additive for all different reasons.These additives can comprise tensio-active agent, defoamer or coatings additive(s), charge control agent, conductive particle or polymkeric substance, thickening material or viscosity modifier, coalescing aid, linking agent or stiffening agent, solubility and/or solid particle dye, antifogging agent, inorganic or organic filler, delustring bead, inorganic or polymer beads, adhesion promoter, Aggressive solvents or chemical etchant, lubricant, softening agent, antioxidant, space agent, tinting material or staining agent, alligatoring agent, surface slip agent, UV absorption agent, index-matching material, fire retardant and other additive well known in the art.
In one particular embodiment, by using suitable linking agent such as melamine resin, glycoluril formaldehyde resins, poly carboxylic acid and acid anhydrides, polyamine, poly-imines, epihalohydrin, epoxide, diepoxide, dialdehyde, glycol, carboxylic acid halide, ketenes, polyaziridine, isocyanic ester, carbodiimide, metal carbonate and their combination to make applied layer be cross-linked.Or, by using radiation such as UV or visible ray, electron beam, plasma body or corona suitably, applied layer is cross-linked.
Anti-fog layer or the first and second binder layers are formed by any method known in the art.Concrete method comprises by any coating process known from the coating of suitable coating composition, and described coating process has such as rod painting, scraper for coating, airblade coating, intaglio plate coating, dip-coating, slot die coating, roller coat, the coating of roller upper blade, spraying etc.Other technology can comprise ink jet printing, intaglio printing, silk screen printing, calendering, laminated, hot-melt extruded etc.Or described one or more layer transfers to acceptor member by the applying of heat and/or pressure from donor member.
With regard to its in tinted shade needed for regard to application, a key property of anti-fog layer of the present invention is its high transparent to visible ray, as indicated by its high transmission of visible light % (%VLT).%VLT is to the volume efficiency of incident light and by such as United States Patent (USP) 7 by the transmitted light of layer, 410, use described in 825 densometer (as X-rite densometer) measure layer optical density (OD) or directly by instrument as BYKGardnerHaze-GardPlus measures.As measured by densometer or BYKGardnerHaze-GardPlus, anti-fog layer of the present invention has the %VLT of at least 40%, preferably at least 50%, more preferably at least 60%, most preferably at least 70% or even at least 90%.
In addition, as the entirety comprising all layers being incorporated into matrix material, transparent composite can have high %VLT.In a particular embodiments, transparent composite can have the %VLT of at least 30%, at least 40%, at least 50%, at least 60% or even at least 80%.
In addition, as measured by Scotch tape test, anti-fog layer can have good adhesion to adjacent layer.Scotch tape test has more detailed description in Examples below part.A special advantage of the present invention is to have good adhesion according to the matrix material of embodiment described herein to layer below.Traditional anti-fog layer locks into the ability of the substrate adhered to below, particularly when not affecting the transparency of anti-fog layer or anti-fog effect negatively.
Also in addition, as, separating layer upper to himself by foldable layer and observed layer whether adhere to himself measure, anti-fog layer can not be clamminess.This minor portion will hereafter describe in more detail.A special advantage of the present invention is have good adhesion according to the matrix material of embodiment as herein described to layer below and be not clamminess in the layer being exposed to environment.Traditional anti-fog layer locks into the ability of the substrate below adhering to while not also being clamminess on opposing surface.
In addition, anti-fog layer is tested by steam bath.Steam bath experimental measurement anti-fog layer bears wet environment repeatedly and the ability of variation without anti-fog effect.A special advantage of the present invention is that can bear washing repeatedly and wet environment repeatedly according to the matrix material of embodiment described herein to expose and without the variation of anti-fog effect, particularly in water-based anti fogging coating composite.
Also in addition, a special advantage of the present invention is matrix material described herein not leafing in flexure process.This attribute quantizes by the flexible operation carrying out 2000 circulations in Gelbo trier.In embodiment described herein, matrix material not leafing after 2000 circulations in Gelbo trier.When customizing matrix material to have required anti-fog effect, the transparency, tackiness and their combination, traditional matrix material locks into leafing.
Transparent composite of the present invention described above can comprise any amount of other functional layer for any object.These functional layers can comprise antistatic layer, undercoat, adhesion promoting layer, flame-retardant layer, blocking layer, air-permeable layer, transport layer, sealing ply, wear-resisting or scrape resistant layer, hard coat, release layer, smooth layer, anti-reflecting layer, refractive index matching layers, UV protective layer, Hue layer, anti-tamper layer etc.
Example
Embodiments of the invention will be illustrated with following instance, and these examples are schematic but not limit the scope of the invention.The polymeric substrates used in these examples or layer comprise (1) polyvinyl chloride (PVC) sheet material and (2) fluorinated ethylene propylene (FEP) the multipolymer sheet material through C-process.
Component for the various layers of example of the present invention and comparative sample comprises following commercially available material:
A kind of aliphatic urethane aqueous dispersion of a.NeorezR9621, DSMNeoresins supply;
A kind of aliphatic urethane aqueous dispersion of b.NeorezR9330, DSMNeoresins supply;
A kind of aliphatic urethane aqueous dispersion of c.NeorezR9679, DSMNeoresins supply;
A kind of aliphatic urethane aqueous dispersion of d.NeorezR600, DSMNeoresins supply;
A kind of aliphatic urethane aqueous dispersion of e.BondthaneUD-410, BPI supply;
A kind of HMMM compound of f.Cymel303LF, CytechIndustires supply; With
A kind of ethoxylated non-ionic fluorochemical surfactant of g.ZonylFSO, Dupont supply;
A kind of colloidal silica dispersion of h.LudoxAM, WRGrace supply;
A kind of fluorinated anionic tensio-active agent of i.CapstoneFS-61, Dupont supply.
Binder layer
The two-layer matrix material of example 1-
The coating composition for binder layer that describes in table 1A to be applied in the FEP substrate of C-process and under 93 degrees Celsius drying with various thickness 10 minutes.Subsequently, the FEP sheet layer of each adhesive coated being incorporated into PVC sheet makes binder layer between FEP and PVC sheet.Laminated or at 40psi under 121 degrees Celsius foot pressure is carried out or is carried out with hand roller under room temperature (RT).Some so obtained matrix materials also solidify the various time period under 107 degrees Celsius.In Instron, press the stripping strength between ASTMD1876 mensuration FEP sheet material and PVC sheet, unit is the every linear inch of pound (PLI).The peel strength value of various composite structure, processing details and correspondence is listed in table 1B.
Table 1A
Table 1B
Matrix material Adhesive sample Adhesive thickness Laminated Additional curing Stripping strength
Micron PLI
Matrix material 1 Tackiness agent 1 2 Roller (RT) 20 minutes 6.7
Matrix material 2 Tackiness agent 2 2 Roller (RT) 20 minutes 5.6
Matrix material 3 Tackiness agent 3 2 Roller (RT) 20 minutes 5.3
Matrix material 4 Tackiness agent 1 2 Foot pressure; 15 seconds - 4.3
Matrix material 5 Tackiness agent 4 2 Roller (RT) 2 minutes 2.4
Matrix material 6 Tackiness agent 4 2 Roller (RT) 3 minutes 2.6
Matrix material 7 Tackiness agent 4 2 Roller (RT) 5 minutes 3.2
Matrix material 8 Tackiness agent 4 2 Roller (RT) 20 minutes 5.2
Matrix material 9 Tackiness agent 4 6 Roller (RT) 2 minutes 3.6
Matrix material 10 Tackiness agent 4 6 Roller (RT) 3 minutes 3.6
Matrix material 11 Tackiness agent 4 6 Roller (RT) 5 minutes 3.5
Matrix material 12 Tackiness agent 5 2 Roller (RT) 20 minutes 5.4
Matrix material 13 Tackiness agent 6 2 Roller (RT) 20 minutes 5.4
Matrix material 14 Tackiness agent 7 2 Roller (RT) 2 minutes 0
Matrix material 15 Tackiness agent 7 2 Roller (RT) 3 minutes 0
Matrix material 16 Tackiness agent 7 2 Roller (RT) 5 minutes 0
Matrix material 17 Tackiness agent 7 2 Roller (RT) 20 minutes 0
Matrix material 18 Tackiness agent 8 2 Roller (RT) 2 minutes 0.5
Matrix material 19 Tackiness agent 8 2 Roller (RT) 3 minutes 0.7
Matrix material 20 Tackiness agent 8 2 Roller (RT) 5 minutes 0.6
As implied above, binder combination tackiness agent 1 to tackiness agent 6 produces the peel strength value of at least 2PLI.
In addition, use each matrix material of tackiness agent 1 to tackiness agent 6 to be bent, folding and flexure and without leafing.On the other hand, adhesion is provided hardly or not with the matrix material that tackiness agent 7 to tackiness agent 8 produces.In fact, tackiness agent 7 to tackiness agent 8 is used can not to produce flexible, folding or flexure and without a composite material of leafing.
Example 2-is based on the 3-layer composite material of tackiness agent 4
To all separately coating tackiness agent 4 dryings 10 minutes under 93 degrees Celsius as shown in Table A 1 on the two sides of two FEP sheet materials of C-process on two sides.With hand roller under room temperature (RT), then under 107 degrees Celsius solidify 5 minutes by laminated for the FEP sheet material of each adhesive coated between two PVC sheet to produce the following matrix material shown in following table 2.In addition, make each matrix material stand in Gelbo device 2000 circulation flexures and inspection layer from.
Table 2
Sample number into spectrum Composite structure Binder layer thickness Whether leafing
Matrix material B1 PVC/ tackiness agent 4/FEP/ tackiness agent 4/PVC 2 microns No
Matrix material B2 PVC/ tackiness agent 4/FEP/ tackiness agent 4/PVC 8 microns No
Example 3-anti-fog layer
On the surface one of anti fogging coating composite as described in the following table 3 to be coated on matrix material B1 and B2 in layer of PVC.In addition, directly anti fogging coating composite is applied to the FEP sheet material independently through C-process.
Table 3
Performance test
The transparency-%VLT is evaluated to the above-mentioned sample it being coated with anti-fog layer.%VLT be at least 50% sample be regarded as " height ", otherwise to be considered as " low ".
Adhere to-there is the anti-fog layer of the sample of anti-fog layer to the adhesion of front one deck with the evaluation of Scotch adhesive tape.Any material removes and is considered to " poor ", and is considered to " good " without removing.
Tackiness-by foldable layer to himself going up and being separated it to evaluate the tackiness of the sample with anti-fog layer.If layer adheres to himself, be then considered as " being clamminess ", otherwise, be considered as " not being clamminess ".
Anti misting capability-anti-fog layer sample be exposed to the steam bath 15 seconds of water temperature 80 degrees Celsius and evaluate anti-fog feature.Wash in warm suds through steaming sample and drying with clean rag subsequently.In the foregoing manner sample is exposed to steam again after drying.Continue 15 times by being exposed to the circulation that then steam wash, and whether sample for reference there is the loss of removing of any material or anti-fog feature.Anti-fog layer of the present invention " passed through " this test, in working cycle or loop ends time do not demonstrate removing or the loss of anti-fog feature of any material.
Leafing-make the matrix material of band antifogging coating stand the flexure of 2000 circulations and evaluate leafing in Gelbo trier.If all leafing do not detected in any layers in office, then think that this sample " has passed through " test.
Test-results is summarized in following table 2B.
Table 2B
As implied above, sample 1-3 and 7 produces has high transparent, good adhesion, not tacky surface, good flexibility, good detergency keep the matrix material tinted shade of good anti-fog performance.On the other hand, sample 4-6 provides poor adhesion or the surface of being clamminess and is considered to for undesirable tinted shade application.
Many different aspects and embodiment are all possible.Some in these aspects and embodiment will be described below.After reading this specification, those of skill in the art should be familiar with, and these aspects and embodiment are only schematic and do not limit the scope of the invention.Embodiment can according to any one in following Listed Items or many persons.
Project 1. 1 kinds of transparent composites, it comprises: stratum basale; And anti-fog layer, wherein said anti-fog layer comprises binder polymer, hard polymer and hydrophilic polymer, and wherein said binder polymer, hard polymer and hydrophilic polymer are different.
Project 2. 1 kinds of transparent composites, it comprises: stratum basale; First binder layer; First transparent layer; Second binder layer; Second transparent layer; And anti-fog layer, described anti-fog layer comprises binder polymer, hard polymer and hydrophilic polymer, and wherein said binder polymer, hard polymer and hydrophilic polymer are different.
Project 3. 1 kinds of anti fogging coating composites, it comprises binder polymer, hard polymer and hydrophilic polymer, and wherein said binder polymer, hard polymer and hydrophilic polymer are different.
The transparent composite of project 4. according to any one of aforementioned project, wherein said binder polymer comprises the polymkeric substance had lower than the Tg of about 45 degrees Celsius; Wherein said hard polymer comprises the polymkeric substance of the pencil hardness as having at least H measured by ASTMD3363; And wherein said hydrophilic polymer comprises the polymkeric substance of the hydrophilic segment having main chain and be covalently bound to described main chain.
The transparent composite of project 5. according to any one of aforementioned project or coating composition, wherein said anti-fog layer or anti fogging coating composite comprise hydrophilic polymer.
The transparent composite of project 6. according to project 4 or coating composition, wherein said hydrophilic polymer comprises hydrophilic polyurethane.
The transparent composite of project 7. according to any one of project 5 to 6 or coating composition, wherein said hydrophilic polymer comprises the polymkeric substance of the hydrophilic segment having polyurethane backbone and be covalently bound to described polyurethane backbone.
The transparent composite of project 8. according to project 7 or coating composition, wherein said hydrophilic segment comprises oxirane, lactone, lactan, silane, acrylamide, alcohol, gelatin or their combination.
The transparent composite of project 9. according to any one of project 7 to 8 or coating composition, wherein said hydrophilic segment comprises oxirane, lactone, lactan or their combination.
The transparent composite of project 10. according to any one of project 7 to 9 or coating composition, wherein said hydrophilic segment has at least about 100, at least about 500 or even at least about 1000 molecular weight.
The transparent composite of project 11. according to any one of project 7 to 10 or coating composition, wherein said hydrophilic segment account for described hydrophilic polymer weight at least about 1 % by weight, at least about 10 % by weight or even at least about 25 % by weight.
The transparent composite of project 12. according to any one of project 5 to 11 or coating composition, wherein based on the overall dry weight of described anti-fog layer or coating composition, described hydrophilic polymer is not with higher than about 99.9 % by weight, not higher than about 90 % by weight, not higher than about 80 % by weight or be not even present in described anti-fog layer higher than the amount of about 70 % by weight.
The transparent composite of project 13. according to any one of project 5 to 12 or coating composition, wherein based on the overall dry weight of described anti-fog layer or coating composition, described hydrophilic polymer is with at least about 0.01 % by weight, at least about 10 % by weight, at least about 20 % by weight or be even present in described anti-fog layer at least about the amount of 25 % by weight.
The transparent composite of project 14. according to any one of project 5 to 13 or coating composition, wherein based on the overall dry weight of described anti-fog layer or coating composition, described hydrophilic polymer is present in described anti-fog layer with the amount in the scope of about 0.01 % by weight to about 99.9 % by weight, about 10 % by weight to about 90 % by weight, about 20 % by weight to about 80 % by weight or even about 25 % by weight to about 75 % by weight.
The transparent composite of project 15. according to any one of aforementioned project, wherein said anti-fog layer or anti fogging coating composite comprise hard polymer.
The transparent composite of project 16. according to project 15 or coating composition, wherein said hard polymer comprises from the obtained polymkeric substance of ethylenically unsaturated monomers or interpretation, and described ethylenically unsaturated monomers comprises vinylbenzene, styrene derivatives, vinylformic acid or derivatives thereof, methacrylic acid or derivatives thereof, alkene, (methyl) vinyl cyanide, methylene-succinic acid and derivative, toxilic acid and derivative thereof, vinyl halide, vinylidene halide, fluoropolymer or their combination.
The transparent composite of project 17. according to any one of project 15 to 16 or coating composition, wherein said hard polymer comprises from the obtained polymkeric substance of the aqueous dispersion of polycondensate.
The transparent composite of project 18. according to any one of project 15 to 17 or coating composition, wherein said hard polymer comprises urethane, polyester or their combination.
The transparent composite of project 19. according to any one of project 15 to 18, wherein said hard polymer comprises from the obtained polymkeric substance of polyurethane dispersions, polyester dispersions or their combination.
The transparent composite of project 20. according to any one of project 15 to 19 or coating composition, wherein as measured by ASTMD3363, described hard polymer has at least about H, at least about 2H, pencil hardness at least about 3H.
The transparent composite of project 21. according to any one of project 15 to 20 or coating composition, wherein as measured by ASTMD412, described hard polymer has at least about 2000psi, at least about 3000psi or even at least about 100% modulus of 3500psi.
The transparent composite of project 22. according to any one of project 15 to 21 or coating composition, wherein as measured by ASTMD412, described hard polymer has not higher than about 15000psi, not higher than about 10000psi or not even higher than 100% modulus of about 7500psi.
The transparent composite of project 23. according to any one of project 15 to 22 or coating composition, wherein as measured by ASTMD412, described hard polymer has at least about 3000psi, at least about 4000psi or even at least about the tensile strength of 5000psi.
The transparent composite of project 24. according to any one of project 15 to 23 or coating composition, wherein as measured by ASTMD412, described hard polymer has not higher than the tensile strength of about 15000psi.
The transparent composite of project 25. according to any one of project 15 to 24 or coating composition, wherein based on the overall dry weight of described anti-fog layer or coating composition, described hard polymer is not with higher than about 90 % by weight, not higher than about 80 % by weight, not higher than about 70 % by weight or be not even present in described anti-fog layer higher than the amount of about 60 % by weight.
The transparent composite of project 26. according to any one of project 15 to 25 or coating composition, wherein based on the overall dry weight of described anti-fog layer or coating composition, described hard polymer is with at least about 0.1 % by weight, at least about 10 % by weight, at least about 20 % by weight or even exist at least about the amount of 25 % by weight.
The transparent composite of project 27. according to any one of project 15 to 26 or coating composition, wherein based on the overall dry weight of described anti-fog layer or coating composition, described hard polymer exists with the amount in the scope of about 0.1 % by weight to about 90 % by weight, about 10 % by weight to about 80 % by weight, about 20 % by weight to about 70 % by weight or even about 25 % by weight to about 60 % by weight.
The transparent composite of project 28. according to any one of aforementioned project or coating composition, wherein said anti-fog layer or coating composition comprise binder polymer.
The transparent composite of project 29. according to project 28 or coating composition, wherein said binder polymer comprises polyester or urethane.
The transparent composite of project 30. according to any one of project 28 to 29 or coating composition, wherein said binder polymer comprises aliphatic nonionic urethane.
The transparent composite of project 31. according to any one of project 28 to 30 or coating composition, wherein based on the overall dry weight of described anti-fog layer or coating composition, described binder polymer is not with higher than about 90 % by weight, not higher than about 80 % by weight, not higher than about 70 % by weight or even exist higher than the amount of about 60 % by weight.
The transparent composite of project 32. according to any one of project 28 to 31 or coating composition, wherein based on the overall dry weight of described anti-fog layer or coating composition, described binder polymer is with at least about 0.1 % by weight, at least about 10 % by weight, at least about 20 % by weight or even exist at least about the amount of 25 % by weight.
The transparent composite of project 33. according to any one of project 28 to 32 or coating composition, wherein based on the overall dry weight of described anti-fog layer or coating composition, described binder polymer exists with the amount in the scope of about 0.1 % by weight to about 90 % by weight, about 10 % by weight to about 80 % by weight, about 20 % by weight to about 70 % by weight or even about 25 % by weight to about 60 % by weight.
The transparent composite of project 34. according to any one of project 28 to 33 or coating composition, wherein said binder polymer comprises from the obtained polymkeric substance of ethylenically unsaturated monomers or interpretation, and described ethylenically unsaturated monomers is selected from vinylbenzene, styrene derivatives, vinylformic acid or derivatives thereof, methacrylic acid or derivatives thereof, alkene, (methyl) vinyl cyanide, methylene-succinic acid and derivative, toxilic acid and derivative thereof, vinyl halide, vinylidene halide, fluoropolymer and their combination.
The transparent composite of project 35. according to any one of project 28 to 34 or coating composition, wherein said binder polymer comprises from the obtained polymkeric substance of fluoropolymer or interpretation, and wherein said fluoropolymer is selected from PTFE, FPA, FEP, THV, ETFE, PVDF and their combination.
The transparent composite of project 36. according to any one of project 28 to 35 or coating composition, wherein said binder polymer comprises from the obtained polymkeric substance of the aqueous dispersion of polycondensate.
The transparent composite of project 37. according to any one of project 28 to 36 or coating composition, wherein said binder polymer comprises from urethane or the obtained polymkeric substance of polyester dispersions.
The transparent composite of project 38. according to any one of aforementioned project or coating composition, wherein said anti-fog layer or coating composition also comprise linking agent.
The transparent composite of project 39. according to any one of aforementioned project or coating composition, wherein said anti-fog layer or coating composition also comprise the cross-linked network of polymkeric substance, and described polymkeric substance comprises hard polymer, hydrophilic polymer and binder polymer.
The transparent composite of project 40. according to any one of aforementioned project or coating composition, wherein said anti-fog layer or coating composition also comprise and are selected from following additive: tensio-active agent, defoamer, coatings additive(s), charge control agent, conductive particle, conductive polymers, thickening material, viscosity modifier, coalescing aid, solubility and/or solid particle dye, antifogging agent, inorganic or organic filler, delustring bead, inorganic or polymer beads, adhesion promoter, Aggressive solvents, chemical etchant, lubricant, softening agent, antioxidant, space agent, tinting material, staining agent, alligatoring agent, surface slip agent, UV absorption agent, index-matching material and their combination.
The transparent composite of project 41. according to any one of aforementioned project, it also comprises the first transparent layer that contiguous described stratum basale is arranged.
The transparent composite of project 42. according to project 41, wherein said first transparent layer comprises fluoropolymer.
The transparent composite of project 43. according to any one of project 41 to 42, wherein said first transparent layer comprises the fluoropolymer through C-process.
The transparent composite of project 44. according to any one of project 41 to 43, it also comprises the second transparent layer that contiguous described first transparent layer is arranged.
The transparent composite of project 45. according to project 44, wherein said second transparent layer comprises fluoropolymer or polyvinyl chloride or polyester or polycarbonate or rhodia or polyolefine.
The transparent composite of project 46. according to any one of project 44 to 45, wherein said second transparent layer comprises the fluoropolymer through C-process.
The transparent composite of project 47. according to any one of project 41 to 46, wherein said first transparent layer and described second transparent layer comprise identical polymer materials.
The transparent composite of project 48. according to any one of aforementioned project, wherein said transparent composite comprises the first binder layer be arranged between described first transparent layer and described stratum basale; And the second binder layer be arranged between described second transparent layer and described first transparent layer.
The transparent composite of project 49. according to project 48, wherein said first binder layer or described second binder layer comprise polyether polyols with reduced unsaturation.
The transparent composite of project 50. according to any one of project 48 to 49, wherein said first binder layer or described second binder layer comprise the crosslinked aliphatic urethane aqueous dispersion of solidification.
The transparent composite of project 51. according to any one of project 48 to 50, wherein said first binder layer or described second binder layer comprise the binder polymer identical with described anti-fog layer.
The transparent composite of project 52. according to any one of project 48 to 51, wherein said first binder layer or described second binder layer comprise the insoluble polymer of water-soluble polymers, lyophilic colloid or the form in latex or dispersion.
The transparent composite of project 53. according to any one of project 48 to 52, wherein said first binder layer or described second binder layer comprise from ethylenically unsaturated monomers polymkeric substance as obtained in vinylbenzene, styrene derivatives, vinylformic acid or derivatives thereof, methacrylic acid or derivatives thereof, alkene, (methyl) vinyl cyanide, methylene-succinic acid and derivative, toxilic acid and derivative thereof, vinyl halide, vinylidene halide or fluoropolymer and interpretation.
The transparent composite of project 54. according to any one of project 48 to 53, wherein said first binder layer or described second binder layer comprise from the obtained polymkeric substance of the aqueous dispersion of polycondensate.
The transparent composite of project 55. according to any one of project 48 to 54, wherein said first binder layer or described second binder layer comprise the polymkeric substance obtained from urethane or polyester dispersions.
The transparent composite of project 56. according to any one of project 48 to 55, described first binder layer or described second binder layer comprise have not higher than 45 degrees Celsius, not higher than 20 degrees Celsius, not higher than 10 degrees Celsius or not even higher than the polymkeric substance of the second-order transition temperature (Tg) of 0 degree Celsius.
The transparent composite of project 57. according to any one of aforementioned project, wherein said matrix material comprises stratum basale.
The transparent composite of project 58. according to any one of aforementioned project, wherein said matrix material comprises the transparent base layer of self-supporting.
The transparent composite of project 59. according to any one of aforementioned project, wherein said matrix material comprises stratum basale, and described stratum basale comprises polyvinyl chloride, polyester, fluoropolymer, polycarbonate or polyolefine.
The transparent composite of project 60. according to any one of aforementioned project, wherein as measured by ASTMD1876, the stripping strength between described first transparent layer and stratum basale is at least about 2 pounds of every linear inches (PLI), at least about 3PLI, at least about 4PLI or even at least about 5PLI.
The transparent composite of project 61. according to any one of aforementioned project, wherein as measured by ASTMD1876, the stripping strength between described second transparent layer and described first transparent layer is at least about 2 pounds of every linear inches (PLI), at least about 3PLI, at least about 4PLI or even at least about 5PLI.
The transparent composite of project 62. according to any one of aforementioned project, wherein as measured by ASTMD1876, the bonding between skin and the layer comprising fluoropolymer has at least about 2 pounds of every linear inches (PLI), at least about 3PLI, at least about 4PLI or even at least about the cohesive strength of 5PLI; And wherein as measured by ASTMD1876, the bonding comprised between the layer of fluoropolymer and the layer comprising polymkeric substance has at least about 2 pounds of every linear inches (PLI), at least about 3PLI, at least about 4PLI or even at least about the cohesive strength of 5PLI.
The transparent composite of project 63. according to any one of aforementioned project, wherein as measured by Scotch tape test, described anti-fog layer has good adhesion to adjacent layer.
The transparent composite of project 64. according to any one of aforementioned project, wherein as upper to himself by folding described layer, be separated described layer also layer as described in observation whether adhere to himself measure, described anti-fog layer is not clamminess.
The transparent composite of project 65. according to any one of aforementioned project, wherein said anti-fog layer is tested by steam bath.
The transparent composite of project 66. according to any one of aforementioned project, wherein as by Gelbo trier bend 2000 circulation measure, described matrix material not leafing.
The transparent composite of project 67. according to any one of aforementioned project, wherein said anti-fog layer has the %VLT of at least 50% or at least 70% or even at least 90%.
Project 68. 1 kinds comprises the transparent composite of anti-fog layer, and wherein said anti-fog layer comprises hydrophilic polymer and antiblocking agent, and described antiblocking agent comprises colloid silica and/or fluorinated anionic tensio-active agent.
Project 69. 1 kinds of anti fogging coating composites, it comprises hydrophilic polymer and antiblocking agent, and described antiblocking agent comprises colloid silica and/or fluorinated anionic tensio-active agent.
The transparent composite of project 70. according to any one of aforementioned project or coating composition, wherein said anti fogging coating composite and/or layer comprise antiblocking agent.
The transparent composite of project 71. according to any one of aforementioned project or coating composition, wherein said anti fogging coating composite and/or layer comprise antiblocking agent, and described antiblocking agent comprises colloid inorganic particle.
The transparent composite of project 72. according to any one of aforementioned project or coating composition, wherein said anti fogging coating composite and/or layer comprise antiblocking agent, and described antiblocking agent comprises colloid silica.
The transparent composite of project 73. according to any one of aforementioned project or coating composition, wherein said anti fogging coating composite and/or layer comprise antiblocking agent, and described antiblocking agent comprises fluorinated surfactant.
The transparent composite of project 74. according to any one of aforementioned project or coating composition, wherein said anti fogging coating composite and/or layer comprise antiblocking agent, and described antiblocking agent comprises fluorinated anionic tensio-active agent.
The transparent composite of project 75. according to any one of aforementioned project or coating composition, wherein said anti fogging coating composite and/or layer comprise antiblocking agent, described antiblocking agent comprises colloid silica, based on the total weight of described anti fogging coating composite or described anti-fog layer, described colloid silica is with at least about 1 % by weight, at least about 3 % by weight or be even present in described anti fogging coating composite or described anti-fog layer at least about the amount of 7 % by weight.
The transparent composite of project 76. according to any one of aforementioned project or coating composition, wherein said anti fogging coating composite and/or layer comprise antiblocking agent, described antiblocking agent comprises colloid silica, and described colloid silica is not with higher than about 50 % by weight, not higher than about 40 % by weight, not higher than about 30 % by weight or be not even present in described anti fogging coating composite or described anti-fog layer higher than the amount of about 20 % by weight.
The transparent composite of project 77. according to any one of aforementioned project or coating composition, wherein said anti fogging coating composite and/or layer comprise antiblocking agent, described antiblocking agent comprises colloid silica, and described colloid silica is present in described anti fogging coating composite or described anti-fog layer with the amount in the scope of about 1 % by weight to about 50 % by weight, about 3 % by weight to about 40 % by weight or even about 7 % by weight to about 30 % by weight.
The transparent composite of project 78. according to any one of aforementioned project or coating composition, wherein said anti fogging coating composite and/or layer comprise antiblocking agent, described antiblocking agent comprises fluorinated anionic tensio-active agent, based on the total weight of described anti fogging coating composite or described anti-fog layer, described fluorinated anionic tensio-active agent is with at least about 0.005 % by weight, at least about 0.01 % by weight or be even present in described anti fogging coating composite or described anti-fog layer at least about the amount of 0.03 % by weight.
The transparent composite of project 79. according to any one of aforementioned project or coating composition, wherein said anti fogging coating composite and/or layer comprise antiblocking agent, described antiblocking agent comprises fluorinated anionic tensio-active agent, and described fluorinated anionic tensio-active agent is not with higher than about 15 % by weight, not higher than about 10 % by weight, not higher than about 8 % by weight or be not even present in described anti fogging coating composite or described anti-fog layer higher than the amount of about 2 % by weight.
The transparent composite of project 80. according to any one of aforementioned project or coating composition, wherein said anti fogging coating composite and/or layer comprise antiblocking agent, described antiblocking agent comprises fluorinated anionic tensio-active agent, and described fluorinated anionic tensio-active agent is present in described anti fogging coating composite or described anti-fog layer with the amount in the scope of about 0.005 % by weight to about 15 % by weight, about 0.01 % by weight to about 10 % by weight or even about 0.03 % by weight to about 8 % by weight.
Note, all behaviors describing in generality or describe in example are not all needs, and a part of specific behavior may not need, and also may perform one or more other behavior except described those.Also in addition, the order that wherein behavior is listed differs and is decided to be its order be performed.
Describe the solution of beneficial effect, other advantage and problem above in conjunction with specific embodiments.But, the solution of beneficial effect, advantage, problem and any beneficial effect, advantage or solution may be made to occur or become more obvious any feature should not be understood as any or all claim crucial, require or required feature.
The generality that specification sheets described herein and embodiment are intended to the structure providing various embodiment is understood.Described specification sheets and signal have no intention to serve as and use the detailed of structure described herein or the device of method and all factors and characteristics of system and comprehensively describe.Divide other embodiment also can provide in combination in single embodiment, conversely, for the various feature described in the context of single embodiment for purpose of brevity also provides discriminably or with any sub-portfolio.In addition, the value addressed in scope mention each value comprised within the scope of this.Other embodiments many may only after reading this specification for apparent those of skill in the art.Can use from the present invention and derive other embodiment, make to do structure replacement, logic is replaced or other changes and does not depart from scope of the present invention.Correspondingly, the present invention should be considered as illustrative and not restrictive.

Claims (15)

1. an anti fogging coating composite, described anti fogging coating composite comprises binder polymer, hard polymer and hydrophilic polymer, and wherein said binder polymer, hard polymer and hydrophilic polymer are different.
2. a transparent composite, described transparent composite comprises:
A. stratum basale; With
B. anti-fog layer, wherein said anti-fog layer comprises binder polymer, hard polymer and hydrophilic polymer, and wherein said binder polymer, hard polymer and hydrophilic polymer are different.
3. comprise a transparent composite for anti-fog layer, wherein said anti-fog layer comprises hydrophilic polymer and antiblocking agent, and described antiblocking agent comprises colloid silica and/or fluorinated anionic tensio-active agent.
4. anti fogging coating composite according to any one of claim 1 to 2 or transparent composite, wherein said binder polymer comprises the polymkeric substance had lower than the Tg of about 45 degrees Celsius; Wherein said hard polymer comprises the polymkeric substance of the pencil hardness as having at least H measured by ASTMD3363; And wherein said hydrophilic polymer comprises the polymkeric substance of the hydrophilic segment having main chain and be covalently bound to described main chain.
5. anti fogging coating composite according to any one of claim 1 to 2 or transparent composite, wherein said hydrophilic polymer comprises the polymkeric substance of the hydrophilic segment having polyurethane backbone and be covalently bound to described polyurethane backbone, and wherein said hydrophilic segment comprises oxirane, lactone, lactan or their combination.
6. anti fogging coating composite according to any one of claim 1 to 2 or transparent composite, wherein:
A. based on the overall dry weight of described anti-fog layer or coating composition, described hydrophilic polymer is present in described anti-fog layer with the amount in the scope of about 10 % by weight to about 90 % by weight;
B. based on the overall dry weight of described anti-fog layer or coating composition, described hard polymer is present in described anti-fog layer with the amount in the scope of about 10 % by weight to about 80 % by weight; With
C. based on the overall dry weight of described anti-fog layer or coating composition, described binder polymer exists with the amount in the scope of about 10 % by weight to about 80 % by weight.
7. anti fogging coating composite according to any one of claim 1 to 2 or transparent composite, wherein said hard polymer comprises from the obtained polymkeric substance of ethylenically unsaturated monomers or interpretation, and described ethylenically unsaturated monomers comprises vinylbenzene, styrene derivatives, vinylformic acid or derivatives thereof, methacrylic acid or derivatives thereof, alkene, (methyl) vinyl cyanide, methylene-succinic acid and derivative, toxilic acid and derivative thereof, vinyl halide, vinylidene halide, fluoropolymer or their combination.
8. anti fogging coating composite according to any one of claim 1 to 2 or transparent composite, wherein as measured by ASTMD3363, described hard polymer has the pencil hardness at least about 2H.
9. anti fogging coating composite according to any one of claim 1 to 2 or transparent composite, wherein said binder polymer comprises polyester or urethane.
10. anti fogging coating composite according to any one of claim 1 to 2 or transparent composite, wherein said anti-fog layer or coating composition also comprise linking agent.
11. transparent composites according to any one of claim 2 to 3, wherein said transparent composite comprises:
A. stratum basale;
B. the first binder layer;
C. the first transparent layer;
D. the second binder layer;
E. the second transparent layer; With
F. anti-fog layer, described anti-fog layer comprises binder polymer, hard polymer and hydrophilic polymer, and wherein said binder polymer, hard polymer and hydrophilic polymer are different.
12. transparent composites according to any one of claim 2 to 3, wherein said transparent composite is the form of personal safety equipment.
13. transparent composites according to any one of claim 2 to 3, wherein said transparent composite comprises:
A. stratum basale;
B. the first binder layer;
C. the first transparent layer;
D. the second binder layer;
E. the second transparent layer; With
F. anti-fog layer; With
G. wherein as measured by ASTMD1876, the stripping strength between described first transparent layer and stratum basale is at least about 2 pounds of every linear inches (PLI), at least about 3PLI, at least about 4PLI or even at least about 5PLI.
14. transparent composites according to any one of claim 2 to 3, wherein as upper to himself by folding described layer, be separated described layer also layer as described in observation whether adhere to himself measure, described anti-fog layer is not clamminess.
15. transparent composites according to any one of claim 2 to 3, wherein
A. described anti-fog layer comprises antiblocking agent, and described antiblocking agent comprises colloid silica, and based on the total weight of described anti-fog layer, described colloid silica is present in described anti-fog layer with the scope of about 3 % by weight to about 40 % by weight; And/or
B. wherein said anti-fog layer comprises antiblocking agent, described antiblocking agent comprises fluorinated anionic tensio-active agent, based on the total weight of described anti-fog layer, described fluorinated anionic tensio-active agent is present in described anti-fog layer with the amount in the scope of about 0.01 % by weight to about 10 % by weight.
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US9346974B2 (en) 2016-05-24

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